Method for coloring keratin fibers

ABSTRACT

The present invention relates to a composition for coloring keratinaceous fibers and a method of using the same. The composition of the present invention contains (a) at least one pyrimidine derivative and (b) at least one compound selected from an m-phenylene derivative, an m-aminophenol derivative, a pyridine derivative, a resorcinol derivative, a methylenedioxybenzene derivative, or 3,4-diaminobenzoic acid or combinations thereof. The method of the present invention includes applying the coloring composition to keratin-containing fibers and subsequently rinsing the coloring composition from the fibers.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a national stage application under 35 U.S.C. § 371of international application PCT/EP99/09901 filed on Dec. 14, 1999, theinternational application not being published in English. Thisapplication also claims priority under 35 U.S.C. §119 to DE 198 59800.9, filed on Dec. 23, 1998.

FIELD OF THE INVENTION

The invention relates to an agent for dyeing keratin fibers, inparticular human hair, which comprises pyrimidine derivatives incombination with special couplers, to the use of this combination asdyeing component in hair dyeing agents, and to a method of dyeingkeratin fibers, in particular human hair.

BACKGROUND OF THE INVENTION

For the dyeing of keratin fibers, e.g. hair, wool or furs, use isgenerally made either of substantive dyes or oxidation dyes which areformed by oxidative coupling of one or more developer component with oneanother or with one or more coupler components. Coupler and developercomponents are also referred to as oxidation dye precursors.

The developer components usually used are primary aromatic amines havinga further free or substituted hydroxyl or amino group in the para orortho position, diaminopyridine derivatives, heterocyclic hydrazones,4-aminopyrazolone derivatives, and 2,4,5,6-tetraaminopyrimidine andderivatives thereof.

Specific representatives are, for example, p-phenylene-diamine,p-toluylenediamine, 2,4,5,6-tetraaminopyrimidine, p-aminophenol,N,N-bis(2-hydroxyethyl)-p-phenylenediamine,2-(2,5-diaminophenyl)ethanol, 2-(2,5-diaminophenoxy)ethanol,1-phenyl-3-carboxyamido-4-aminopyrazol-5-one, 4-amino-3-methylphenol,2-aminomethyl-4-aminophenol, 2-hydroxymethyl-4-aminophenol,2-hydroxy-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidineand 2,5,6-triamino-4-hydroxypyrimidine.

The coupler components usually used are m-phenylene-diamine derivatives,naphthols, resorcinol and resorcinol derivatives, pyrazolones andm-aminophenols. Particularly suitable as coupler substances areα-naphthol, 1,5-, 2,7- and 1,7-dihydroxynaphthaline,5-amino-2-methylphenol, m-aminophenol, resorcinol, resorcinol monomethylether, m-phenylenediamine, 2,4-diaminophenoxyethanol,1-phenyl-3-methylpyrazol-5-one, 2,4-dichloro-3-aminophenol,1,3-bis(2,4-diaminophenoxy)propane, 2-chlororesorcinol,4-chlororesorcinol, 2-chloro-6-methyl-3-aminophenol, 2-methylresorcinoland 5-methylresorcinol.

German patent application DE-Al-41 15 148 discloses oxidation dyeingagents which, in a cosmetic carrier, comprise a2,4,5,6-tetraaminopyrimidine or a 6-hydroxy-2,4-triaminopyridine asoxidation base (developer) and a combination of certain green couplersand violet couplers for producing brilliant and washfast blackcolorations.

With regard to further customary dye components, reference is madespecifically to the “Dermatology” series, published by Ch. Culnan, H.Maibach, Verlag Marcel Dekker Inc., New York, Basle, 1986, vol. 7, Ch.Zviak, The Science of Hair Care, chapter 7, pages 248-250 (substantivedyes), and chapter B, pages 264-267 (oxidation dyes), and the “EuropeanInventory of Cosmetic Raw Materials”, 1996, published by the EuropeanCommission, available in diskette format from the Bundesverband derdeutschen Industrie-und Handelsunternehmen für Arzneimittel, Reformwarenund Körperpflegemittel e.V., Mannheim.

Although intensive colorations with good fastness properties can beachieved with oxidation dyes, the development of the color, however,generally takes place under the influence of oxidizing agents, such as,for example, H₂O₂, which in some cases can result in damage to thefibers. Furthermore, some oxidation dye precursors or certain mixturesof oxidation dye precursors can occasionally have a sensitizing effectin people with sensitive skin. Although substantive dyes are appliedunder more moderate conditions, their disadvantage is that thecolorations frequently have inadequate fastness properties.

It is an object of the present invention to provide a dyeing agent forkeratin fibers, in particular human hair, which is oxidizable byatmospheric oxygen, i.e. is not necessarily dependent on oxidizingagents, such as, for example, H₂O₂. The agent should be able to beapplied to the fibers in a simple manner and, with regard to depth ofcolor, gray coverage and fastness properties, are at least equal inqualitative terms to otherwise customary oxidation hair dyeing agents.Moreover, the dyeing agents must have no, or only a very low,sensitizing potential. It was a further object to find a dyeing systemthat allows blue shades to be produced on the keratin fiber bycomponents specifically matched to one another.

SUMMARY OF THE INVENTION

Surprisingly, it has now been found that pyrimidine derivatives incombination with special couplers are highly suitable for the dyeing ofkeratin fibers, even in the absence of oxidizing agents i.e. in thepresence of atmospheric oxygen. They produce colorations with excellentbrilliance and depth of color and lead to a wide variety of colorshades. However, the use of oxidizing agents should not in principle beexcluded here.

The invention provides an agent for the dyeing of keratin fibers, inparticular human hair, comprising

A) at least one pyrimidine derivative of the general formula I

 in which R¹, R², R³ and R⁴ may be identical or different and arehydrogen, OH, NH₂ or a group NR⁵R⁶, in which R⁵ and R⁶ may be identicalor different and are C₁-C₄-alkyl, C₁-C₄-hydroxyalkyl having a primaryand/or secondary hydroxyl group,

where two of the radicals R¹, R², R³ or R⁴ together can form anoptionally substituted 5- and 6-membered heterocycle containing one ortwo nitrogen and/or oxygen atom(s) in the molecule,

with the proviso that at least two of the radicals R¹, R², R³ or R⁴ area group NH₂ and/or NR⁵R⁶,

B) at least one compound chosen from the group consisting of

(a) m-phenylene derivatives of the formulae II and III

 in which R⁷ and R⁸ may be identical or different and are hydrogen,C₁-C₄-alkyl or C₁-C₄-hydroxyalkyl,

R⁹ is C₁-C₄-hydroxyalkyl or a radical of the general formula IV

 in which R⁷ and R⁸ are as defined above and m is an integer from 1 to4,

R¹⁰ is hydrogen or a radical of the general formula V

 in which R⁷ and R⁹ are as defined above and n is an integer from 1 to4,

R¹¹ is hydrogen, C₁-C₄-alkyl or C₁-C₄-hydroxyalkyl,

(b) m-aminophenol derivatives

 in which R¹² is hydrogen or C₁-C₄-alkyl,

R¹³ is hydrogen, fluorine, chlorine, OCH₃ or C₁-C₄-alkyl,

R¹⁴ is hydrogen, C₁-C₄-alkyl, C₁-C₄-hydroxyalkyl or OCF₃,

R¹⁵ is hydrogen, fluorine, chlorine or OCH₃,

with the provisos that R¹², R¹³, R¹⁴ and R¹⁵ are not hydrogen at thesame time and that, if R¹² is methyl, R¹³, R¹⁴ and R¹⁵ are not hydrogenat the same time,

(c) pyridine derivatives of the formulae VII and VIII

 in which R¹⁶ and R¹⁷ may be identical or different and are fluorine,chlorine or OCH₃,

 in which R¹⁸ is hydrogen, C₁-C₄-alkyl or C₁-C₄-hydroxyalkyl,

R¹⁹ is OH or NH₂,

R²⁰ is hydrogen, C₁-C₄-alkoxy or NH₂,

X is hydrogen or OCH₃,

with the provisos that, if R¹⁹ is NH₂, R¹⁸ and R²⁰ are not C₁-C₄-alkylor methoxy respectively at the same time, and if R¹⁸ is hydrogen, R¹⁹and R²⁰ are not OH or hydrogen respectively at the same time,

(d) resorcinol derivatives of the formula IX

 in which R²¹, R²² and R²³ may be identical or different and arehydrogen, C₁-C₄-alkyl or C₁-C₄-hydroxyalkyl,

with the provisos that R²¹, R²² and R²³ are not hydrogen at the sametime, if R²¹ and R²³ are hydrogen, R²² is not methyl, and if R²¹ ismethyl, R²² and R²³ are not hydrogen at the same time,

(e) methylenedioxybenzene derivatives of the formula X

 in which R²⁴ is OH, NH₂ or NHR²⁵, in which R²⁵ is C₁-C₄-alkyl orC₁-C₄-hydroxyalkyl, and

(f) 3,4-diaminobenzoic acid.

DETAILED DESCRIPTION OF THE INVENTION

Keratin fibers are to be understood as meaning wool, furs, feathers and,in particular, human hair. In principle, however, the dyes according tothe invention may also be used for the dyeing of other natural fibers,such as, for example, cotton, jute, sisal, linen or silk, modifiednatural fibers, such as, for example, regenerated cellulose, nitro-,alkyl- or hydroxyalkyl- or acetylcellulose, and synthetic fibers, suchas, for example, polyamide, polyacrylonitrile, polyurethane andpolyester fibers.

The pyrimidine derivatives of the formula I used according to theinvention are preferably chosen from the group consisting of4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-2,5,6-triaminopyrimidine,2,4,5,6-tetraaminopyrimidine, 5,6-diamino-2,4-dihydroxypyrimidine,2,4-diamino-5,6-dihydroxypyrimidine,4-dimethylamino-2,5,6-tetraminopyrimidine. Particular preference isgiven to using 2,4,5,6-tetraaminopyrimidine,4-dimethylamino-2,5,6-tetraminopyrimidine,4-hydroxy-2,5,6-triaminopyrimidine and5,6-diamino-2,4-dihydroxypyrimidine.

These substances are known from the literature or are availablecommercially.

The aforementioned pyrimidine derivatives of the formula I arepreferably used in the agents according to the invention in an amount offrom 0.03 to 65 mmol, in particular from 1 to 40 mmol, based on 100 g ofthe total dyeing agent.

Of the compounds of the formula VIII, preference is given to those inwhich X is hydrogen.

Couplers of component B are preferably chosen from the group1,3-bis(2,4-diaminophenoxypropane), 1,3-bis(2,4-diaminophenylpropane),2,4-diaminophenoxyethanol, 2,6-bis(2′-hydroxyethylamino)toluene,3-amino-2-chloro-6-methylphenyl, 5-amino-4-chloro-2-methylphenol,2,9-dichloro-3-aminophenol, 3,5-diamino-2,6-dimethoxypyridine,5-methylresorcinol, 2,5-dimethylresorcinol, 3,4-methylenedioxyphenol,3,4-methylenedioxyaniline, N-(2-hydroxyethyl)-3,4-methylenedioxyanilineand any mixtures of the above.

The aforementioned compounds of component B can be used in an amount of,in each case, 0.03 to 65 mmol, in particular 1 to 40 mmol, in each casebased on 100 g of the total dyeing agent.

In all of the dyeing agents it is also possible to use two or moredifferent pyrimidine derivatives of the formula I together; likewise, itis also possible to use two or more different compounds of component Btogether. This embodiment also covers the use of substances whichrepreses reaction products of pyrimidine derivatives of the formula Iwith said compounds of component B.

The color shades can also be further varied and intensified if one ormore compounds chosen from 5,6-dihydroxyindole and its N-substitutedC₁-C₄-alkyl and C₁-C₄-hydroxyalkyl derivatives, 5,6-dihydroxyindolineand its N-substituted C₁-C₄-alkyl and C₁-C₄-hydroxyalkyl derivatives andthe compounds known as developers, chosen from the group consisting ofp-phenylenediamine, p-tolylenediamine, p-aminophenol,4,4′-diaminodiphenylamine,1,10-bis(2,5-diaminophenyl)-1,4,7,10-tetraoxydecane, 2,(2′-hydroxyethyl)-p-phenylenediamine, 2,6-dichloro-4-aminophenol,N,N-bis(2′-hydroxyethyl)-p-phenylenediamine, 3-methyl-4-aminophenol,2-aminomethyl-4-aminophenol, 5-aminosalicylic acid,bis(2-hydroxy-5-aminophenyl)methane and 2-(2,5-diamino-phenoxy)ethanolare added to the agent according to the invention.

A further preferred developer component is4-amino-2-((diethylamino)methyl)phenol.

Particularly preferred developer components are, for example,p-phenylenediamine, p-tolylenediamine,1,10-bis(2,5-diaminophenyl)-1,4,7,10-tetraoxydecane, 2,(2′-hydroxyethyl)-p-phenylenediamine, 2,6-dichloro-4-aminophenol,N,N-bis(2′-hydroxyethyl)-p-phenylenediamine, 3-methyl-4-aminophenol,2-aminomethyl-4-aminophenol, 4-amino-2-((diethylamino)methyl)phenol andbis(2-hydroxy-5-aminophenyl)methane.

In a further preferred embodiment, activated carbonyl compounds andfurther substances known as developers or couplers are added to thecombination according to the invention of components A and B to furthermodify the color shades.

Examples of activated carbonyl compounds are isatin, 5-chloroisatin,5-bromoisatin, 6-bromoisatin, 5-nitroisatin, N-hydroxymethylisatin,N-allylisatin, 5-isatinsulfonic acid Na salt, glutaconaldehydetetrabutylammonium salt, tribase aldehyde, malonaldehyde bis(dimethylacetal), 4-hydroxy-3-methoxycinnanaldehyde, 1-piperidinomethylisatin,1-diethylaminomethylisatin, glutaconaldehyde Na salt,5-N-methylanilinopentadienyl, 2-chloro-3-hydroxy-methylene-1-cyclohexene1-aldehyde, N-(5-anilino-2,4-pentanedien-1-ylidene)anilinium chloride,trans-p-(2-furyl)acrolein, 2-nitro-1,3-indanedione, dehydroascorbicacid, 2-acetyl-1,3-cyclohexanedione,7-dimethylamino-2,4,6-heptatrienylidene dimethylammonium perchlorate and4-formyl-1-methylpyridinium benzenesulfonate.

Examples of couplers which may additionally be present are3-amino-2-methylamino-6-methoxypyridine,2-amino-4-(2′-hydroxyethylamino)anisole, α-naphthol, resorcinol,resorcinol monomethyl ether, 4-chlororesorcinol, 2-methylresorcinol,m-aminophenol, 3-N,N-dimethylaminophenol, 5-amino-2-methoxyphenol,5-amino-2-methylphenol, 3-amino-2,4-dimethylphenol,3-(N-cyclopentyl)aminophenol, 1,5-, 1,7-, 2,7-dihydroxynaphthalenes,o-aminophenol, 6-hydroxybenzomorpholine, 1-phenyl-3-methylpyrazol-5-one,2-amino-6-methylphenol, 2,6-dihydroxy-3,4-dimethylpyridine,4-hydroxyindole, 6-hydroxyindole, 7-hydroxyindole, 4-aminoindole and2,4-diamino-5-methylphenetole.

The dyeing agent according to the invention represents an air-oxidizablesystem. In this connection, it is possible to dispense with additionaloxidizing agents, e.g. H₂O₂. In some circumstances, however, it may bedesirable to add hydrogen peroxide or other oxidizing agents, such asperoxydisulfate or percarbonate, to the agents according to theinvention to achieve shades which are paler than keratin fibers to bedyed. Furthermore, in some circumstances, it is possible, in the absenceof oxidizing agents, i.e. whether atmospheric oxygen or hydrogenperoxide is used, to establish different color shades. Oxidizing agentsare generally used in an amount of from 0.01 to 6% by weight, based onthe use solution. An oxidizing agent preferred for human hair is H₂O₂.

Furthermore, it is possible to carry out the oxidation using enzymes.Here, the enzymes can be used either to generate oxidizing percompounds,and to intensify the effect of a small amount of oxidizing agentpresent. Examples of enzymatic processes are the use of laccases and theintensification of the effect of small amounts (e.g. 1% and less, basedon the total agent) of hydrogen peroxide by peroxidases.

In a preferred embodiment, the dyes according to the invention comprise,for the further modification of the color shades, in addition to thecompounds present according to the invention, additionally customarysubstantive dyes, e.g. from the group of nitrophenylenediamines,nitroaminophenols, anthraquinones or indophenols, such as, for example,the compounds known under the international designations or trade namesHC Yellow 2, HC Yellow 4, HC Yellow 6, Basic Yellow 57, Disperse Orange3, HC Red 3, HC Red BN, Basic Red 76, HC Blue 2, Disperse Blue 3, BasicBlue 99, HC Violet 1, Disperse Violet 1, Disperse Violet 4, DisperseBlack 9, Basic Brown 16 and Basic Brown 17, and also picramic acid,2-amino-6-chloro-4-nitrophenol,4-amino-2-nitrodiphenylamine-2′-carboxylic acid,6-nitro-1,2,3,4-tetrahydroquinoxaline,4-N-ethyl-1,4-bis(2′-hydroxyethylamino)-2-nitrobenzene hydrochloride and1-methyl-3-nitro-4-(2′-hydroxyethyl)aminobenzene. The inventive agentsaccording to this embodiment preferably comprise the substantive dyes inan amount of from 0.01 to 20% by weight, based on the total dyeingagent.

Furthermore, the preparations according to the invention can alsocomprise naturally occurring dyes such as, for example, henna red, hennaneutral, henna black, camomile blossom, sandalwood, black tea, buckthornbark, sage, logwood, madder root, catechu, sedre and alkanna root.

It is not necessary for the oxidation dye precursors or the optionallypresent substantive dyes to each represent uniform compounds. Rather, itis possible that, as a result of the preparation processes for theindividual dyes, further components are present in minor amounts in thedyeing agents according to the invention, provided these do notadversely impair the dyeing result, or have to be excluded for otherreasons, e.g. toxicological reasons.

The dyeing agents according to the invention produce intensivecolorations even at physiologically compatible temperatures of less than45° C. They are therefore particularly suitable for the dyeing of humanhair. For use on human hair, the dyeing agents can usually beincorporated into a hydrous cosmetic carrier. Suitable hydrous cosmeticcarriers are e.g. creams, emulsions, gels and also surfactant-containingfoaming solutions such as e.g. shampoos or other preparations which aresuitable for use on the keratin. fibers. If necessary, it is alsopossible to incorporate the dyeing agents into anhydrous carriers.

Furthermore, the dyeing agents according to the invention can compriseall active ingredients, additives and auxiliaries known in suchpreparations. In many cases, the dyeing agents comprise at least onesurfactant, where, in principle, both anionic and also zwitterionic,ampholytic, nonionic and cationic surfactants are suitable. However, inmany cases it has proven advantageous to choose the surfactants fromanionic, zwitterionic or nonionic surfactants.

Suitable anionic surfactants in preparations according to the inventionare all anionic surface-active substances suitable for use on the humanbody. These are characterized by a solubilizing anionic group, such as,for example, a carboxylate, sulfate, sulfonate or phosphate group and alipophilic alkyl group having about 10 to 22 carbon atoms. Additionally,glycol or. polyglycol ether groups, ester, ether and amide groups andhydroxyl groups may be present in the molecule. Examples of suitableanionic surfactants are, in each case in the form of the sodium,potassium or ammonium and the mono-, di- and trialkanolammonium saltshaving 2 or 3 carbon atoms in the alkanol group,

linear fatty acids having 10 to 22 carbon atoms (soaps)

ether carboxylic acids of the formula R—O—(CH₂—CH₂O)_(x)—CH₂—COOH, inwhich R is a linear alkyl group having 10 to 22 carbon atoms and x=0 or1 to 16,

acyl sarcosides having 10 to 18 carbon atoms in the acyl group,

acyl taurides having 10 to 18 carbon atoms in the acyl group,

acyl isethionates having 10 to 18 carbon atoms in the acyl group,

sulfosuccinic mono- and dialkyl esters having 8 to 18 carbon atoms inthe alkyl group and sulfosuccinic monoalkylpolyoxyethyl esters having 8to 18 carbon atoms in the alkyl group and 1 to 6 oxyethyl groups,

linear alkanesulfonates having 12 to 18 carbon atoms,

linear alpha-olefinsulfonates having 12 to 18 carbon atoms,

alpha-sulfo fatty acid methyl esters of fatty acids having 12 to 18carbon atoms,

alkyl sulfates and alkylpolyglycol ether sulfates of the formulaR—O(CH₂—CH₂O)_(x)—SO₃H, in which R is a preferably linear alkyl grouphaving 10 to 18 carbon atoms and x=0 or 1 to 12,

mixtures of surface-active hydroxysulfonates according to DE-A-37 25030,

sulfated hydroxyalkyl polyethylene and/or hydroxyalkylene propyleneglycol ethers according to DE-A-37 23 354,

sulfonates of unsaturated fatty acids having 12 to 24 carbon atoms and 1to 6 double bonds according to DE-A-39 26 344,

esters of tartaric acid and citric acid with alcohols, which representaddition products of approximately 2 to 15 molecules of ethylene oxideand/or propylene oxide to fatty alcohols having 8 to 22 carbon atoms.

Preferred anionic surfactants are alkyl sulfates, alkylpolyglycol ethersulfates and ether carboxylic acids having 10 to 18 carbon atoms in thealkyl group and up to 12 glycol ether groups in the molecule, and inparticular salts of saturated and in particular unsaturatedC₈-C₂₂-carboxylic acids, such as oleic acid, stearic acid, isostearicacid and palmitic acid.

Zwitterionic surfactants is the term used for those surface-activecompounds which carry at least one quaternary ammonium group and atleast one —COO⁽⁻⁾— or —SO₃ ⁽⁻⁾ group in the molecule. Particularlysuitable zwitterionic surfactants are the betaines, such as theN-alkyl-N,N-dimethylammonium glycinates, for example thecocoalkyldimethylammonium glycinate,N-acyl-amminopropyl-N,N-dimethylammonium glycinates, for example thecocoacylaminopropyldimethylammonium glycinate, and2-alkyl-3-carboxymethyl-3-hydroxyethylimidazolines having in each case 8to 18 carbon atoms in the alkyl or acyl group, and cocoacylaminoethylhydroxyethylcarboxymethylglycinate. A preferred zwitterionic surfactantis the fatty acid amide derivative known under the CTFA nameCocamidopropyl Betaine.

Ampholytic surfactants are understood as meaning those surface-activecompounds which, apart from a C₈₋₁₈-alkyl or -acyl group in themolecule, contain at least one free amino group and at least one —COOHor —SO₃H group and are capable of forming internal salts. Examples ofsuitable ampholytic surfactants are N-alkylglycines, N-alkylpropionicacids, N-alkylaminobutyric acids, N-alkylaminodipropionic acids,N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines,N-alkylsarcosines, 2-alkylaminopropionic acids and alkylam inoaceticacids having in each case about 8 to 18 carbon atoms in the alkyl group.Particularly preferred ampholytic surfactants areN-cocoalkylaminopropionate,, cocoacylaminoethylaminopropionate andC₁₂₋₁₈-acylsarcosine.

Nonionic surfactants comprise, as hydrophilic group, e.g. a polyolgroup, a polyalkylene glycol ether group or a combination of polyol andpolyglycol ether group. Such compounds are, for example,

addition products of 2 to 30 mol of ethylene oxide and/or 0 to 5 mol ofpropylene oxide to linear fatty alcohols having 8 to 22 carbon atoms, tofatty acids having 12 to 22 carbon atoms and to alkyl phenols having 8to 15 carbon atoms in the alkyl group,

C₁₂₋₂₂-fatty acid mono- and diesters of addition products of from 1 to30 mol of ethylene oxide to glycerol,

C₈₋₂₂-alkyl mono- and oligoglycosides and ethoxylated analogs thereof,

addition products of from 5 to 60 mol of ethylene oxide to castor oiland hydrogenated castor oil,

addition products of ethylene oxide to sorbitan fatty acid esters

addition products of ethylene oxide to fatty acid alkanolamides.

Examples of the cationic surfactants to be used in the hair-treatmentagents according to the invention are, in particular, quaternaryammonium compounds. Preference is given to ammonium halides, such asalkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides andtrialkylmethylammonium chlorides, e.g. cetyltrimethylammonium chloride,stearyltrimethylammonium chloride, distearyldimethylammonium chloride,lauryldimethylammonium chloride, lauryldimethylbenzylammonium chlorideand tricetylmethylammonium chloride. Further cationic surfactants whichcan be used according to the invention are the quaternized proteinhydrolysates.

Likewise suitable for the invention are cationic silicone oils, such as,for example, the commercially available products Q2-7224 (manufacturer:Dow Corning; a stabilized trimethylsilylamodimethicone), Dow Corning 949emulsion (comprising a hydroxylamino-modified silicone, which is alsoreferred to as amodimethicone), SM-2059 (manufacturer: GeneralElectric), SLM-55067 (manufacturer: Wacker) and Abil®-Quat 3270 and 3272(manufacturer: Th. Goldschmidt; diquaternary polydimethylsiloxanes,Quaternium-80).

Alkylamidoamines, in particular fatty acid amidoamines, such asstearylamidopropyldimethylamine obtainable under the name Tego Amid®S18, are distinguished not only by. a good conditioning action, butspecifically by their good biodegradability.

Likewise very biodegradable are quaternary ester compounds, “esterquats”, such as the. methylhydroxyalkyldialkoyloxyalkylammoniummethosulfates sold under the trade name Stepantex®.

An example of a quaternary sugar derivative which: can be used ascationic surfactant is the commercial product Glucquat® 100, accordingto CTFA nomenclature a “Lauryl Methyl Gluceth-10 Hydroxypropyl DimoniumChloride”.

The compounds containing alkyl groups which are used as surfactants mayeach be uniform substances. However, it is generally preferred to startfrom natural vegetable or animal raw materials for the preparation ofthese substances, thus giving substance mixtures having varying alkylchain lengths depending on the respective raw material.

In the case of the surfactants which represent additional products ofethylene and/or propylene oxide to fatty alcohols or derivatives ofthese addition products, it is possible to use either products with a“normal” homolog distribution, or those with a narrowed homologdistribution. “Normal” homolog distribution is understood as meaninghere mixtures of homologs obtained during the reaction of fatty alcoholand alkylene oxide using alkali metals, alkali metal hydroxides oralkali metal alkoxides as catalysts. Narrowed homolog distributions are,by contrast, obtained if, for example, hydrotalcites, alkaline earthmetal salts of ether carboxylic acids, alkaline earth metal oxides,hydroxides or alkoxides are used as catalysts. The use of productshaving narrowed homolog distribution may be preferable.

Further active ingredients, auxiliaries and additives are, for example,

nonionic polymers such as, for example, vinyloyrrolidone/vinyl acrylatecopolymers, polyvinylpyrrolidone and vinylpyrrolidone/vinyl acetatecopolymers and polysiloxanes,

cationic polymers, such as quaternized cellulose ethers, polysiloxanescontaining quaternary groups, dimethyldiallylammonium chloride polymers,acrylamide-dimethyldiallylammonium chloride copolymers,dimethylaminoethyl methacrylatevinylpyrrolidone copolymers quaternizedwith diethyl sulfate, vinylpyrrolidoneimidazolinium methochloridecopolymers and quaternized polyvinyl alcohol,

zwitterionic and amphoteric polymers such as, for example,acrylamidopropyltrimethylammonium chloride/acrylate copolymers andoctylacrylamide/methyl methacrylate/tert-butylaminoethylmethacrylate/2-hydroxypropyl methacrylate copolymers,

anionic polymers such as, for example, polyacrylic acids, crosslinkedpolyacrylic acids, vinyl acetate/crotonic acid copolymers,vinylpyrrolidonelvinyl acrylate copolymers, vinyl acetate/butylmaleate/isobornyl acrylate copolymers, methyl vinyl ether/maleicanhydride copolymers and acrylic acid/ethylacrylate/N-tert-butylacrylamide terpolymers,

thickeners, such as agar agar, guar gum, alginates, xanthan gum, gumarabic, karaya gum, carob bean flour, linseed gums, dextrans, cellulosederivatives, e.g. methylcellulose, hydroxyalkylcellulose andcarboxymethylcellulose, starch fractions and derivatives such asamylose, amylopectin and dextrins, clays such as, for example, bentoniteor fully synthetic hydrocolloids such as, for example, polyvinylalcohol,

structurants, such glucose and maleic acid,

hair-conditioning compounds, such as phospholipids, for example soyalecithin, egg lecithin and cephalins, and silicone oils,

protein hydrolysates, in particular elastin, collagen, keratin, milkprotein, soya protein and wheat protein hydrolysates, condensationproducts thereof with fatty acids, and quaternized protein hydrolysates,

perfume oils, dimethyl isosorbide and cyclodextrins,

solubility promoters, such as ethanol, isopropanol, ethylene glycol,propylene glycol, glycerol and diethylene glycol,

antidandruff agents, such as Piroctone Olamine and Zinc Omadine,

further substances for adjusting the pH,

active ingredients, such as panthenol, pantothenic acid, allantoin,pyrrolidonecarboxylic acids and salts thereof, plant extracts andvitamins,

cholesterol,

light protection agents,

consistency regulators, such as sugar esters, polyol esters or polyolalkyl ethers,

fats and waxes, such as spermaceti, beeswax, montan wax, paraffins,fatty alcohols and fatty acid esters,

fatty acid alkanolamides,

complexing agents, such as EDTA, NTA and phosphonic acids,

swelling and penetration substances, such as glycerol, propylene glycolmonoethyl ether, carbonates, hydrogencarbonates, guanidines, ureas, andprimary, secondary and tertiary phosphates, imidazoles, tannins,pyrrole,

opacifiers, such as latex,

pearlizing agents, such as ethylene glycol mono- and distearate,

propellants, such as propane/butane mixtures, N₂O, dimethyl ether, CO₂and air, and

antioxidants.

The constituents of the hydrous carrier are used for the preparation ofthe dyeing agents according to the invention in amounts customary forthis purpose; e.g. emulsifiers are used in concentrations of from 0.5 to30% by weight, and thickeners are used in concentrations of from 0.1 to25% by weight, of the total dyeing agent.

For the dyeing result, it may be advantageous to add ammonium or metalsalts to the dyeing agents. Suitable metal salts are e.g. formates,carbonates, halides, sulfates, butyrates, valerates, caproates,acetates, lactates, glycolates, tartrates, citrates, gluconates,propionates, phosphates and phosphonates of alkali metals, such aspotassium, sodium or lithium, alkaline earth metals, such as magnesium,calcium, strontium or barium, or of aluminum, manganese, iron, cobalt,copper or zinc, preference being given to sodium acetate, lithiumbromide, calcium bromide, calcium gluconate, zinc chloride, zincsulfate, magnesium chloride, magnesium sulfate, ammonium carbonate,chloride and acetate. These salts are preferably present in an amount offrom 0.03 to 65 mmol, in particular from 1 to 40 mmol, based on 100 g ofthe total dyeing agent.

The pH of the ready-to-use dyeing preparations is usually between 2 and11, preferably between 5 and 9.

The present invention further provides for the use of a combination of

A) at least one pyrimidine derivative of the general formula I

 in which R¹, R², R³ and R⁴ may be identical or different and arehydrogen, OH, NH₂ or a group NR⁵R⁶, in which R⁵ and R⁶ may be identicalor different and are C₁-C₄-alkyl, C₁-C₄-hydroxyalkyl having a primaryand/or secondary hydroxyl group, where two of the radicals R¹, R², R³ orR⁴ together can form an optionally substituted 5- and 6-memberedheterocycle containing one or two nitrogen and/or oxygen atom(s) in themolecule,

with the proviso that at least two of the radicals R¹, R², R³ or R⁴ area group NH₂ and/or NR⁵R⁶,

B) at least one compound chosen from the group consisting of the (a)m-phenylenediamine derivatives of the general formulae II or III, (b)m-aminophenol derivatives of the general formula VI, (c) pyridinederivatives of the formulae VII or VIII, (d) resorcinol derivatives ofthe formula IX, (e) methyldioxybenzene derivatives of the formula X or(f) 3,4-diaminobenzoic acid, which are shown above,

for dyeing keratin fibers.

The present invention also further provides a method of dyeing keratinfibers, in particular human hair, in which a dyeing agent comprising

A) at least one pyrimidine derivative of the general formula I,

 in which R¹, R², R³ and R⁴ may be identical or different and arehydrogen, OH, NH₂ or a group NR⁵R⁶, in which R⁵ and R⁶ may be identicalor different and are C₁-C₄-alkyl, C₁-C₄-hydroxyalkyl having a primaryand/or secondary hydroxyl group, where two of the radicals R¹, R², R³ orR⁴ together can form an optionally substituted 5- and 6-memberedheterocycle containing one or two nitrogen and/or oxygen atom(s) in themolecule,

with the proviso that at least two of the radicals R¹, R², R³ or R⁴ area group NH₂ and/or NR⁵R⁶,

B) at least one compound chosen from the group consisting of the (a)m-phenylenediamine derivatives of the general formulae II or III, (b)m-aminophenol derivatives of the general formula VI, (c) pyridinederivatives of the formulae VII or VIII, (d) resorcinol derivatives ofthe formula IX, (e) methyldioxybenzene derivatives of the formula X or(f) 3,4-diaminobenzoic acid,

and customary cosmetic ingredients, is applied to the keratin fibers,left on the fibers for a while, usually about 30 minutes, and thenrinsed out again or washed out using a shampoo.

The pyrimidine derivatives of the formula I and the compounds ofcomponent B can either be applied to the hair simultaneously or oneafter the other, it being unimportant which of the two components isapplied first. If it is necessary to achieve a certain color shade, anyoxidizing agent used is also applied. in this stage together with theother components, or subsequently. The optionally present ammonium ormetal salts may be added to the first or the second component. There maybe an interval of up to 30 minutes. between application of the firstcomponent- and that of the second component. Pretreatment of the fiberswith the salt solution is also possible.

EXAMPLES

Hair dyeing agents according to the invention were in the form of a hairdyeing cream emulsion of the composition given in Table 1.

TABLE 1 1 2 3 4 5 6 7 Component % by wt. C₁₂-C₁₄-fatty 20.0 20.0 20.020.0 20.0 20.0 20.0 alcohol + 2 EO sulfate, Na salt, 28% strengthsolution Cocoamidopropyl- 12.5 12.5 12.5 12.5 12.5 12.5 12.5 betaine,30% strength C₁₀-C₁₈ fatty alcohol 2.0 2.0 2.0 2.0 2.0 2.0 2.0 Tallowfatty alcohol 8.5 8.5 8.5 8.5 8.5 8.5 8.5 C₁₆-C₁₈ fatty 0.75 0.75 0.750.75 0.75 0.75 0.75 alcohol + 20 EO Ammonium sulfate 0.1 0.1 0.1 0.1 0.10.1 0.1 Sodium sulfate 0.1 0.1 0.1 0.1 0.1 0.1 0.1 4-Hydroxy-2,5,6-tri-2.4 2.4 2.4 2.4 2.4 2.4 2.4 aminopyrimidine sulfate 2,4-Diaminophenoxy-2.4 — — — — — — ethanol dihydrochloride 3,5-Diamino-2,6-di- — 2.4 — — —— — methoxypyridine dihydrochloride 1,3-bis(2,4-Diamino- — — 4.7 2.121.18 — — phenoxy)propane tetra- hydrochloride N-Allylisatin — — — 0.190.94 — — 1,10-bis(2,5-Diamino- — — — 1.02 5.1 — —phenyl)-1,4,7-10-tetra- oxydecane tetrahydro- chloride3-Amino-2-chloro-6- — — — — — 1.58 — methylphenol 3,4-Methylenedioxy- —— — — — — 1.38 phenol Water ad 100

The individual constituents were mixed together at 70° C. and, aftercooling, adjusted to a pH of 9.5 with NaOH.

Using the compositions given in Table 1, colorations were carried outusing H₂O₂ as oxidizing agent and without oxidizing agent, i.e. by airoxidation.

For the oxidative development of the coloration using H₂O₂, thecompositions shown in Table 1 were mixed with 12% strength hydrogenperoxide in the ratio 1:1. In the case of air oxidation, thecompositions shown in Table 1 were mixed with water prior to use in theratio 1:1.

The application mixture was applied to approximately 15 cm-long tressesof standardized, 90% gray human hair which has not been pretreated inany particular way, and left there for 30 minutes at 27° C. When thedyeing process was complete, the hair was rinsed, washed with acustomary shampoo and then dried. The coloring results are shown inTable 2.

TABLE 2 Color shade Formulation No. H₂O₂ oxidation Air oxidation 1 Deepblue-violet Deep blue-violet 2 Reddish mid-brown Reddish mid-brown 3Mid-dark brown Mid-dark brown 4 — Dark brown 5 — Black 6 Gray magentaRich Bordeaux 7 Pale orange Sand-colored

The dyeing results show that the agents according to the inventionproduce excellent coloring results both with and without the addition ofoxidizing agents. Similar colorations are obtained if, in example 7, theenzyme system glucose-oxidase/glucose/peroxidase or the enzyme systemuricase/uric acid/peroxidase is used as oxidizing agent at pH 8.5.

What is claimed is:
 1. A method of coloring keratin fibers comprisingapplying to keratin fibers a coloring composition formed from componentscomprising A, at least one pyrimidine derivative of formula I

 wherein R¹, R², R³ and R⁴ are, independently of one another, selectedfrom hydrogen, an OH group, a NH₂ group, or a NR⁵R⁶ group, wherein R⁵and R⁶ are independently selected from a C₁ to C₄ alkyl group, or a C₁to C₄ hydroxyalkyl group having one or more hydroxyl groups that areprimary, secondary or combinations thereof, or where two of the R¹, R²,R³ or R⁴ substituents together form a 5 or 6 member, optionallysubstituted, heterocycle ring containing one or two nitrogen atoms, orone or two oxygen atoms or a combination of both in the heterocyclering, with the proviso that at least two of the R¹, R², R³ or R⁴substituents are a NH₂ group or NR⁵R⁶ group, and B at least one Compoundselected from a m-phenylene derivatives of formula II or III

 wherein R⁷, R⁸ and R¹¹ are independently from one another hydrogen, aC₁ to C₄ alkyl group or a C₁ to C₄ hydroxyalkyl group, R⁹ is a C₁ to C₄hydroxyalkyl group or a radical of formula IV

 in which R⁷ and R⁸ are defined as above and m is an integer from 1 to4, and R¹⁰ is hydrogen or a radical of formula V

 in which R⁷ and R⁸ are as defined above and n is an integer from 1 to4, b. m-aminophenol derivatives of formula (VI)

 wherein R¹² is hydrogen or a C₁ to C₄ alkyl group, R¹³ is hydrogen,fluorine, chlorine, an OCH₃ group or a C₁ to C₄ alkyl group, R¹⁴ ishydrogen, a C₁ to C₄ alkyl group, a C₁ to C₄ hydroxyalkyl group or anOCF₃ group, R¹⁵ is hydrogen, fluorine, chlorine or an OCH₃ group, withthe provisos that R¹², R¹³, R¹⁴ and R¹⁵ are not hydrogen at the sametime, and that, if R¹² is methyl, R¹³, R¹⁴ and R¹⁵ are not hydrogen atthe same time, c. pyridine derivatives of formula VII or VIII

 wherein R¹⁶ and R¹⁷ are independently fluorine, chlorine or an OCH₃group, R¹⁸ is hydrogen, a C₁ to C₄ alkyl group or a C₁ to C₄hydroxyalkyl group, R¹⁹ is an OH group or NH₂ group, R²⁰ is hydrogen, aC₁ to C₄ alkoxy group or a NH₂ group, X is hydrogen or an OCH₃ group,with the provisos that, if R¹⁹ is NH₂, R¹⁸ and R²⁰ are not a C₁ to C₄alkyl group and a methoxy group, respectively, at the same time, and ifR¹⁸ is hydrogen, R¹⁹ and R²⁰ are not an OH group and hydrogen,respectively, at the same time, d. resorcinol derivatives of formula IX

 wherein R²¹, R²² and R²³ are independently from one another hydrogen, aC₁ to C₄ alkyl group or a C₁ to C₄ hydroxyalkyl group, with the provisosthat R²¹, R²² and R²³ are not hydrogen at the same time, R²² is notmethyl if R²¹ and R²³ are hydrogen, and R²² and R²³ are not hydrogen atthe same time if R²¹ is methyl, e. methylenedioxybenzene derivatives offormula X

 wherein R²⁴ is an OH group, a NH₂ group or a NHR²⁵ group, in which R²⁵is a C₁ to C₄ alkyl group or a C₁ to C₄ hydroxyalkyl, or f.3,4-diaminobenzoic acid, and combinations thereof; and C. oxidativelydeveloping the coloring composition using atmospheric oxygen, an enzymecontaining system, or combinations thereof as the sole oxidizing agent.2. The method of claim 1 wherein the pyrimidine derivative is4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-2,5,6-triaminopyrimidine,2,4,5,6-tetraaminopyrimidine, 5,6-diamino-2,4-hydroxypyrimidine,2,4-diamino-5,6-dihydroxypyrimidine, or4-methylamino-2,5,6-tetraminopyrimidine, or combinations thereof.
 3. Themethod of claim 2 wherein the pyrimidine derivative is2,4,5,6-tetraaminopyrimidine.
 4. The method of claim 2 wherein thepyrimidine derivative is present in the coloring composition in anamount of from 0.03 mmol to 65 mmol, based on 100 g of the coloringcomposition as a whole.
 5. The method of claim 1 wherein at least one ofR⁷ and R⁸ of the Formula III is a C₁ to C₄ alkyl group or a C₁ to C₄hydroxyalkyl group, and wherein R²⁰ of the Formula VIII is hydrogen or aC₁ to C₄ alkoxy group.
 6. The method of claim 1 wherein the component Bcomprises 1,3-bis(2,4-diaminophenoxypropane),1,3-bis(2,4-diaminophenylpropane), 2,4-diaminophenoxyethanol,2,6-bis(2′-hydroxyethylamino)toluene, 3-amino-2-chloro-6-methylphenol,5-amino-4-chloro-2-methylphenol, 2,4-dichloro-3-aminophenol,3,5-diamino-2,6-dimethoxypyridine, 5-methylresorcinol,2,5-dimethylresorcinol, 3,4-methylenedioxyphenol,3,4-methylenedioxyaniline, orN-(2-hydroxyethyl)-3,4-methylenedioxyanillne, or combinations thereof.7. The method of claim 6 wherein each compound of component B is presentin the coloring composition in an amount of 0.03 mmol to 65 mmol, basedon 100 g of the coloring composition as a whole.
 8. The method of claim1 wherein the coloring composition further comprises at least oneactivated carbonyl compound selected from the group consisting ofisatin, 5-chloroisatin, 5-bromoisatin, 6-bromoisatin, 5-nitroisatin,N-hydroxymethylisatin, N-allylisatin, 5-isatinsulfonic acid Na salt,glutacoldehyde tetrabutylammonium salt, tribase aldehyde, malonaldehydebis(dimethyl acetal), 4-hydroxy-3-methoxycinnanaldehyde,1-piperidinomethylisatin, 1-diethylaminomethylisatin, glutaconaldehydeNa salt, 5-N-methylanilinopentadienyl,2-chloro-3-hydroxymethylene-1-cyclohexene 1-aldehyde,N-(5-anilino-2,4-pentanedien-1-ylidene)anilinium chloride,trans-β-(2-furyl)acrolein, 2-nitro-1,3-indanedione, dehydroascorbicacid, 2-acetyl-1,3-cyclohexanedione,7-dimethylamino-2,4,6-heptatrienylidene dimethylammonium perchlorate,4-formyl-1-methylpyridinium benzenesulfonate, and combinations thereof.9. The method of claim 1 wherein the coloring composition furthercomprises one or more compounds selected from 5,6-dihydroxyindole or itsN-substituted C₁ to C₄ alkyl or C₁ to C₄ hydroxyalkyl derivatives, or5,6-dihydroxyindoline or its N-substituted C₁ to C₄ alkyl orC₁-C₄-hydroxyalkyl derivatives or combinations thereof.
 10. The methodof claim 1 wherein the coloring composition further comprises one ormore compounds selected from p-phenylenediamine, p-tolylenediamine,p-aminophenol, 4,4′-diaminodiphenylamine,1,10-bis(2,5-diaminophenyl)-1,4,7,10-tetraoxydecane,2,(2′-hydroxyethyl)-p-phenylenediamine, 2,6-dichloro-4-aminophenol,N,N-bis(2′-hydroxyethyl)-p-phenylenediamine, 3-methyl-4-aminophenol,2-aminomethyl-4-aminophenol, 5-aminosalicylic acid,bis(2-hydroxy-5-aminophenyl)methane, or 2-(2,5-diaminophenoxy)ethanol,or combinations thereof.
 11. The method of claim 1 wherein the coloringcomposition further comprises anionic surfactants, zwitterionicsurfactants, nonionic surfactants, or combinations thereof.
 12. Themethod of claim 1 wherein the coloring composition is combined with anenzyme containing system before the application of the coloringcomposition to the keratin fibers.